Phosphate activators for cyclohexenone herbicides

ABSTRACT

A biocide composition comprises an effective amount of a biocide and an effective amount of a biocide activator selected from the group consisting of an alkyl phosphate, an alkenyl phosphate, a hydroxyalkyl phosphate, a polyoxyalkylene alkyl ether phosphate, a salt thereof, a polyoxyalkylene alkenyl ether phosphate, a salt thereof, a polyoxyalkylene hydroxyalkyl ether phosphate and a salt thereof.

This is a division of Ser. No. 07/428,072, filed Oct. 25, 1989, nowabandoned, which is a continuation-in-part of Ser. No. 07/042,545, filedApr. 24, 1987 now abandoned which is a continuation of Ser. No.06/725,028, filed Apr. 19, 1985, now abandoned.

The present invention relates to an activator for biocides.

Biocides such as insecticides, germicides, herbicides and plant growthregulators have been used in the form of an emulsion, wettable powder,flowable product, grains or powder.

The physical properties of the biocides have been modified variously soas to exhibit the activity of the active ingredient sufficiently.However, it has been impossible to further increase the effects of thebiocide.

It is quite significant to further increase the effects of knownbiocides, since the development of new biocides is now very difficult.

After intensive investigations, the inventors have found that specifiedcompounds are effective in further activating various biocides. Thepresent invention has been completed on the basis of this finding.

The invention provides a biocide composition which comprises aneffective amount of a biocide and an effective amount of a biocideactivator selected from the group consisting of an alkyl phosphate, analkenyl phosphate, a hydroxyalkyl phosphate, a polyoxyalkylene alkylether phosphate, a salt thereof, a polyoxyalkylene alkenyl etherphosphate, a salt thereof, a polyoxyalkylene hydroxyalkyl etherphosphate and a salt thereof. The invention may be provided in the formof an emulsion concentrate which comprises 10 to 70 weight percent ofthe biocide and 10 to 50 weight percent of the biocide activator, 3 to20 weight percent of an emulsifier and 10 to 50 percent weight of anorganic solvent, or a dilute composition which comprises 100 to 5,000ppm of the biocide, 200 to 10,000 ppm, preferably 500 to 5,000 ppm, ofthe biocide activator and a carrier for dilution. The diluentcomposition is usually prepared just in advance to use thereof.

The alkyl phosphates, polyoxyalkylene alkyl ether phosphates and saltsof them according to the present invention may be prepared by knownprocesses. For example, they are obtained by reacting an alcohol (ifnecessary, after addition of an alkylene oxide thereto) with phosphoruspentoxide and, if necessary, neutralizing the reaction product.

The starting alcohol has 1 to 22 carbon atoms and contains astraight-chain or branched alkyl group, an alkenyl group having doublebond(s) or hydroxyl group(s) in the chain or a hydroxyalkyl group. Thealcohol contains preferably 4 to 18 carbon atoms, 0 to 4, preferably 0to 2 double bonds and 0 to 4, preferably 0 to 2, hydroxyl groups. Thealcohols include, for example, butanol, 2-ethylhexanol, lauryl alcohol,stearyl alcohol and oleyl alcohol.

The alkylene oxides to be added to the alcohol to form a polyoxyalkylenechain include ethylene oxide, propylene oxide and butylene oxide. Theymay be used either alone or in the form of block or random adducts oftwo or more of them. The mol number of addition is 1 to 100, preferably1 to 50.

The addition reaction may be carried out by a known process by, forexample, introducing an alkylene oxide into an alcohol in the presenceof an acid or alkaline catalyst at 50° to 200° C. under 1 to 5 kg/cm².The alcohol or polyoxyalkylene alkyl ether may be phosphated by variousprocesses. For example, 3 mol of the alcohol or polyoxyalkylene alkylether is reacted with 1 mol of phosphorus pentoxide at 80° to 100° C.for about 6 h to obtain a corresponding phosphate easily. The obtainedalkyl phosphate or polyoxyalkylene alkyl ether phosphate is a mixture ofa monoester and a diester in substantially equal amounts. Thoughexcellent effects are exhibited when the activator for biocides of thepresent invention is any of the monoester and the diester, particularlyexcellent effects are obtained when it is a monoester, particularly apolyoxyalkylene alkyl ether/phosphoric monoester or a salt thereof.

When said phosphate is neutralized with a base, a correspondingpolyoxyalkylene alkyl ether phosphate salt is obtained. This ester saltalso has an excellent activating effect. The salts include alkali metal,alkaline earth metal, monoethanolamine, diethanolamine, triethanolamineand ammonium salts.

When the activator for biocides of the present invention is used incombination with a biocide, the effect of the biocides can be increased2 or 3-folds irrespective of the variety of the biocide.

The activator of the present invention is used in an amount of 0.05 to20, preferably 1 to 15 parts by weight per part by weight of thebiocide.

The biocide may be in the form of any of an emulsion, flowable product,wettable powder and powder. Therefore, other additives such as anemulsifying agent, dispersant and carrier may be incorporated thereinaccording to the form of the biocide.

The activator of the present invention may be used by incorporating thesame into the biocide of the above-mentioned form according to theformulation or by applying the same to a subject in combination with thebiocide at the time of the application of the biocide in a diluted form.The activating effect according to the invention can be obtained in bothcases.

Though the mechanism of such a remarkable activation of the biocide bythe activator of the present invention has not been fully elucidatedyet, it may be presumed that the activator for biocide of the presentinvention has an extremely high power of solubilizing the biocideirrespective of the structure of the biocide and, therefore, the biocideis finely divided and the penetration thereof through the surfaces ofplants or into insects and germs is accelerated.

The present invention provides also a biocidal process characterized byspraying an emulsion (or dispersion) of a biocide containing theabove-described activator.

Examples of the biocides which are activated by the activator of thepresent invention will be given below, which by no means limit thebiocides to be activated according to the present invention. Theactivator of the present invention can be used safely without damagingthe farm products. The insecticides include pyrethroid insecticides suchas Fenvalerate[α-cyano-3-phenoxybenzyl-2-(4-chlorophenyl)-3-methylvalerate] andPyrethroid[cyano(4-fluoro-3-phenoxyphenylmethyl-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate];organophosphorus insecticides such as DDVP (2,2-dichlorovinyldimethylphosphate), Sumithion (dimethyl-4-nitro-m-tolylphosphorothionate),Malathon {S-[1,2-bis(ethoxycarbonyl)ethyl]dimethylphosphorothiolthionate}, Dimethoate[dimethyl-S-(N-methylcarbamoylmethyl)phosphorothiol thionate), Elsan{S-[α-(ethoxycarbonyl)benzyl]dimethylphosphorothiol thionate) and Baycid[O,O-dimethyl-O-(3-methyl-4-methylmercaptophenyl)thiophosphate];carbamate insecticides such as Bassa (O-butylphenyl methylcarbamate),MTMC (m-tolyl methylcarbamate), Meobal(3,4-dimethylphenyl-N-methylcarbamate), NAC(1-naphthyl-N-methylcarbamate); as well as Methomyl{methyl-N[(methylcarbamoyl)oxy]thioacetimide} and Cartap{1,3-bis(carbamoylthio)-2-(N,N-dimethylamino)propane hydrochloride].

Examples of acaricides include Smite{2-[2-(p-tert-butylphenoxy)isopropoxy]isopropyl-2-chloroethyl sulfide},Acricid (2,4-dinitro-6-sec-butylphenyl dimethylacrylate), Chlormit(isopropyl 4,4-dichlorobenzylate), Acar (ethyl 4,4-dichlorobenzylate),Kelthane [1,1-bis(p-chlorophenyl)-2,2,2-trichloroethanol], Citrazon(ethyl O-benzoyl-3-chloro-2,6-dimethoxybenzohydroxymate), Plictran(tricyclohexyltin hydroxide) and Omite[2-(p-tert-butylphenoxy)cyclohexyl-2-propinyl sulfite].

Examples of the germicides include organosulfur germicides such asDithane (zinc ethylenebisdithiocarbamate), maneb (manganeseethylenebisdithiocarbamate), thiuram [bis(dimethylthiocarbamoyl)disulfide], Benlate [methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate], Difolatan(N-tetrachloroethylthio-4-cyclohexane-1,2-dicarboxyimide), Daconol(tetrachloroisophthalonitrile), Pansoil(5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole),Thiophanate-methyl[1,2-bis(3-methoxycarbonyl-2-thioureido)-benzene],Rabcide (4,5,6,7,-tetrachlorophthaloid), Kitazin P(O,O-diisopropyl-S-benzyl phosphorothioate), Hinosan(O-ethyl-S,S-diphenyldithiophosphate) and Propenazol(3-allyloxy-1,2-benzothiazole 1,1-dioxide).

Examples of the herbicides include Stam (3,4-dichloropropionanilide),Saturn [S-(4-chlorobenzyl) N,N-diethylthiolcarbamate), Lasso(2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide), Glyphosate[N-(phosphonomethyl)glycine isopropylamine salt], DCMU[3-(3,4-dichlorophenyl)-1,1-dimethylurea), Gramoxone(1,1'-dimethyl-4,4'-dipyridium dichloride, Cloproxydim((E,E)-(+)-2-[1-(3-chloro-2-propenyl)-(oxyimino)propyl]-5-[2-(ethylthio)-propyl]-3-hydroxy-2-cyclohexen-1-one)and Sethoxydim(2-[1-Ethoxyimino)butyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one.

Examples of the plant growth regulating agents include MH (maleic acidhydrazide) and Ethrel (2-chloroethylphosphonic acid).

EXAMPLES AND EFFECTS

The following examples will further illustrate the activators forbiocides of the present invention.

EXAMPLE 1

A compound of the present invention was dissolved in a commerciallyavailable herbicide (Karmex wettable powder, Simazine wettable powder,Paraquat solution or Glyphosate solution) to obtain a 0.2% solution. 10ml of the solution was sprayed to each pot of crabgrass (a weed ofGramineae) which had been grown uniformly. The herbicidal effects ofthem were compared with one another. The crabgrasses used were in athree- or four-foliate period having a height of about 10 cm. Each pothad 25 crabgrasses. The dilution rate of said Karmex wettable powder,Simazine wettable powder, Paraquat solution of Glyphosate solution was1/300. The herbicidal rate was determined by weighing theabove-the-ground parts of the crabgrasses 10 days after the spraying andthe results were represented by percentage based on the weight ofuntreated grasses. The results are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                      Herbicidal rate (%)                                                           Karmex   Simazine Paraquat                                                                           Glyphosate                                             wettable powder                                                                        wettable powder                                                                        solution                                                                           solution                             __________________________________________________________________________    Activator of the present invention                                            POE(3) 2-ethylhexyl phosphate                                                                   84.0     67.2     98.2 100                                  POE(3) POP(5) 2-ethylhexyl                                                                      80.8     68.5     99.1 100                                  phosphate                                                                     POE(3) POP(5) 2-ethylhexyl                                                                      81.0     68.9     99.0 100                                  phosphate/diethanolamine                                                      POE(10) octyl phosphate                                                                         78.4     70.5     100  100                                  Potassium POE(10) octyl                                                                         79.8     72.4     100  100                                  phosphate                                                                     POE(30) lauryl phosphate                                                                        85.7     80.2     100  100                                  POE(30) lauryl phosphate                                                                        86.0     81.5     100  100                                  monoethanolamine                                                              POE(60) POB(10) palmityl                                                                        78.8     82.4     100  100                                  phosphate                                                                     Sodium POE(60) POB(10) palmityl                                                                 72.1     82.0     100  100                                  phosphate                                                                     POE(25) POP(10) oleyl phosphate                                                                 89.1     89.5     100  100                                  Ammonium POE(25) POP(10) oleyl                                                                  89.5     87.8     100  100                                  phosphate                                                                     POE(80) linoleyl phosphate                                                                      88.4     88.1     100  100                                  Calcium POE(80) linoleyl phosphate                                                              89.4     89.9     100  100                                  2-Ethylhexyl phosphate                                                                          69.0     60.0     95.0 97.2                                 Lauryl phosphate  70.1     72.5     90.4 90.0                                 Oleyl phosphate   75.2     79.0     94.0 92.0                                 No activator used 21.0     18.4     64.2 68.4                                 Comparative                                                                   POE(3) 2-ethylhexyl ether                                                                       51.2     42.8     69.0 70.0                                 POE(10) octyl ether                                                                             49.0     40.4     72.0 78.4                                 POE(30) lauryl ether                                                                            52.5     54.5     72.0 80.5                                 POE(25) POP(10) oleyl ether                                                                     57.5     52.8     79.5 75.5                                 POE(60) POB(10) palmityl ether                                                                  45.4     42.1     72.8 75.6                                 POE(80) linoleyl ether                                                                          60.5     55.2     79.2 80.0                                 __________________________________________________________________________     Note:                                                                         Symbols POE, POP and POB represent polyoxyethylene, polyoxypropylene and      polyoxybutylene, respectively. The numerals in the parentheses represent      the mol number of addition.                                              

EXAMPLE 2

Third-instar larvae of plant hoppers were cultured and the insecticidaleffects of insecticides thereon were examined by the leaf dipping method3 repetition. Each group consisted of 10 larvae. The insecticidaleffects were compared with those in an untreated group 24 h after thetreatment. The results are shown in Table 2.

The insecticides used were a Sumithion emulsion and a Malathon emulsioneach diluted to a concentration of 1/2000. The concentration of theactivator of the present invention was controlled to 0.1% based on thediluted emulsion.

                  TABLE 2                                                         ______________________________________                                                             Insecticidal rate (%)                                                         50%                                                                           Sumi-  50%                                                                    ithion Malathon                                                               emulsion                                                                             emulsion                                          ______________________________________                                        Activator of the present invention                                            POE(3) 2-ethylhexyl phosphate                                                                        84.5     80.5                                          POE(3) POP(5) 2-ethylhexyl phosphate                                                                 82.5     78.4                                          POE(3) POP(5) 2-ethylhexyl phosphate                                                                 82.5     78.5                                          diethanolamine                                                                POE(10) octyl phosphate                                                                              80.5     80.0                                          Potassium POE(10) octyl phosphate                                                                    81.2     78.9                                          POE(30) lauryl phosphate                                                                             86.4     82.4                                          POE(30) lauryl phosphate monoethanola-                                                               86.9     86.7                                          mine                                                                          POE(60) POB(10) palmityl phosphate                                                                   78.5     80.0                                          Sodium POE(60) POB(10) palmityl phos-                                                                82.4     81.5                                          phate                                                                         POE(25) POP(10) oleyl phosphate                                                                      90.1     94.6                                          Ammonium POE(25) POP(10) oleyl                                                                       86.5     90.0                                          phosphate                                                                     POE(80) linoleyl phosphate                                                                           89.5     92.1                                          Calcium POE(80) linoleyl phosphate                                                                   90.5     92.6                                          2-Ethylhexyl phosphate 68.2     60.0                                          Lauryl phosphate       75.1     72.0                                          Linoleyl phosphate     85.1     80.0                                          No activator used      49.0     40.0                                          Comparative                                                                   POE(3) 2-ethylhexyl ether                                                                            52.5     41.5                                          POE(10) octyl ether    55.0     40.5                                          POE(30) lauryl ether   55.5     42.8                                          POE(25) POP(10) oleyl ether                                                                          49.0     39.5                                          POE(60) POB(10) palmityl ether                                                                       50.5     40.0                                          POE(80) linoleyl ether 56.0     45.2                                          ______________________________________                                    

EXAMPLE 3

Male imagines of two-spotted red spider were applied to leaf disks ofkidney beans in three replications. Each group consisted of 30 imagines.After the culture at 25° C. for 24 h. 0.2 ml per each group of a testsample was sprayed by the chromatospray method. The insecticidal ratewas determined by comparison with the results of an untreated group 24 hafter the treatment. The acaricides used were Amitraz emulsion andOsadan wettable powder diluted to a concentration of 1/2000. Theconcentration of the activator of the present invention was controlledto 0.1% based on the diluted product. The results are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                                             Insecticidal rate (%)                                                         20%    20%                                                                    Amitraz                                                                              Osadan                                                                 emulsion                                                                             emulsion                                          ______________________________________                                        Activator of the present invention                                            POE(3) 2-ethylhexyl phosphate                                                                        92.5     100                                           POE(3) POP(5) 2-ethylhexyl phosphate                                                                 96.0     100                                           POE(3) POP(5) 2-ethylhexyl phosphate                                                                 96.0     100                                           diethanolamine                                                                PIE(10) octyl phosphate                                                                              98.0     95.4                                          Potassium POE(10) octyl phosphate                                                                    98.5     99.0                                          POE(30) lauryl phosphate                                                                             97.5     100                                           POE(30) lauryl phosphate monoethanola-                                                               90.0     100                                           mine                                                                          POE(60) POB(10) palmityl phosphate                                                                   95.0     100                                           Sodium POE(60) palmityl phosphate                                                                    92.5     100                                           POE(25) POP(10) oleyl phosphate                                                                      100      100                                           Ammonium POE(25) POP(10) oleyl phos-                                                                 100      100                                           phate                                                                         POE(80) linoleyl phosphate                                                                           100      100                                           Calcium POE(80) linoleyl phosphate                                                                   100      100                                           No activator used      58.2     64.2                                          ______________________________________                                    

It is apparent from Examples 1 to 3 that the activators of the presentinvention have an excellent activating effect. In addition, eachcomposition as prepared in Examples 1 to 3 was diluted with water. Theobtained dilute one was effective to improve the biocide activity. Eachcomponent content in the dilute compositions is given below.

In the compositions of Example 1

    ______________________________________                                               activator     2000 ppm                                                        Karmex        1660                                                            Simazine      1660                                                            Paraquat       800                                                            Round-Up       660                                                     ______________________________________                                    

In the compositions of Example 2

    ______________________________________                                               activator     1000 ppm                                                        Sumithion      250                                                            Malathon       250                                                     ______________________________________                                    

In the compositions of Example 3

    ______________________________________                                               activator      1000 ppm                                                       Dani-Cut        100                                                           Osadan          225                                                    ______________________________________                                    

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:
 1. An agriculturalherbicidal composition which consists essentially of an effective amountof an agricultural chemical herbicide and an effective amount of asubstance for increasing the herbicidal rate of said herbicide, saidherbicide being selected from the group consisting of(E,E)-(+)-2-[1-(3-chloro-2-propenyl)-(oxyimino)propyl]-5-[2-(ethylthio)-propyl]-3-hydroxy-2-cyclohexen-1-oneand2-[1-ethoxyimino)butyl]-5-[2(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-oneand said substance being selected from the group consisting of alkylphosphates, alkenyl phosphates, hydroxyalkyl phosphates, andpolyoxyalkylene hydroxyalkyl ether phosphates and salts thereof, saidsubstance having from 1 to 22 carbon atoms in the alkyl, alkenyl orhydroxyalkyl group thereof, the weight ratio of said substance/saidherbicide being in the range of 1/1 to 15/1.
 2. A composition as claimedin claim 1, in which said substance has 1 to 100 oxyalkylene units andthe alkylene group therein has 2, 3 or 4 carbon atoms.
 3. A compositionas claimed in claim 1, in which each of said phosphates is a monoesterof phosphoric acid.
 4. A composition as claimed in claim 1 in which saidsubstance is selected from the group consisting of, oleyl phosphate,and, stearyl phosphate.
 5. A composition as claimed in claim 1, whereinsaid herbicide is(E,E)-(+)-2-[1-(3-chloro-2-propenyl)-(oxyimino)propyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-oneand said substance is an polyoxyalkylene hydroxyalkyl ether phosphate.6. An agricultural herbicidal composition which consists essentially ofan effective amount of an agricultural chemical herbicide, an effectiveamount of a substance for increasing the herbicical rate of saidherbicide and an inert carrier, said herbicide being selected from thegroup consisting of(E,E)-(+)-2-[1-(3-chloro-2-propenyl)-(oxyimino)propyl]-5-[2-(ethylthio)-propyl]-3-hydroxy-2-cyclohexen-1-oneand2-[1-(ethoxyimino)-butyl]-5-[2-(ethylthio)-propyl]-3-hydroxy-2-cyclohexen-1-oneand said substance being selected from the group consisting of alkylphosphates, alkenyl phosphates, hydroxyalkyl phosphates andpolyoxyalkylene hydroxyalkyl ether phosphates and salts thereof, saidsubstance having from 1 to 22 carbon atoms in the alkyl, or alkenyl orhydroxyalkyl group thereof, the weight ratio of said substance/saidherbicide being in the range of 1/1 to 15/1.
 7. A composition as claimedin claim 6, which consists essentially of 100 to 5,000 ppm, based on thecomposition, of said herbicide, from 200 to 10,000 ppm, based on thecomposition, of said substance and the balance is an inert carrier.
 8. Acomposition as claimed in claim 6, wherein said herbicide is(E,E)-(+)-2-[1-(3-chloro-2-propenyl)-(oxyimino)propyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-oneand said substance is an polyoxyalkylene hydroxyalkyl ether phosphate.9. A method of controlling weeds which comprises applying to a weedgrowth medium a herbicidally effective amount of a composition asdefined in claim 1.